Manufacture of azo dyestuffs derived from 2-hydroxynaphthalene-3-carboxylic-acid-arylamides



Patented Mar. 29, 1927.

1,622,690 PATENT OFFICE.

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MANUFACTURE OF AZO DYESTUFFS DERIVED FROM 2 -HYDIl-OXYNAPH'IHALENE-8- CARBOXYLIG-ACID-ABYLAMIDES.

R0 Drawing.

According to-U. S. Patent No. 1,034,853 of Winter et al. granted August6, '19 12, dyestuffs of good pro erties are obtained b the combination 0diam-compounds wit arylides of the 2.3-h droxynaphthoic acid. Now it hasbeen foun that dyestuffs of surrisingly'. favourable pro erties areobtained E the combination of'dlazo compounds derived from mononucleararomatic amines with o-toluidides of 2.3-hydroxynaphthoic acid. Thecompounds containing halogen and among these the compounds containinghalogen in both components are distinguished by their excellent fastnessproper- 'ties.-

v The new azo dyestufls are represented by the general formulacitwhereinR ma be any mononuclear aromatic residue, may be hydrogen,halogen or anv substituent, and Y is a methyl group in (at 0 position tothe nitrogen. pon reduction with stannous chlorid and hydrochloric acidan aromatic amino and a toluidide of l-amino-2-hydroxy-3-naphthoic acidare produced.

An advantage of these dyestufis as compared with the anilido andnitranili'do compounds of 2.3-hydro'xynaphthoic acid as well as with thecompounds cited in great number in the U. S. Patent No. 1,034,853

consists in that they have a great kier-boiL ing and a much betterdischargeability so that a remarkably good white is obtainable.Moreover, thenew dyestuffs possess a very pure shade. As compared withthe compounds of other toluidides' of 2.3-hydroxynaphthoic acid, thoseof the o-toluidides show besides other at least eqtually good propertiesin numerous cases a etter fastness to light. But the special importanceof this invention resides in the discovery of. a

' field of use for o-toluidine and o-nitrotoluene respectively-This'substance is formed, as it is known, as the chief product bynitrating toluene. For the homologues occurring in small quantityespecially p-nitrotoluone great domains of utilization are knownalready, whereas for the chief substance, the

Application and Karen 17, 1922. Serial No. 544,618.

HEISSUD o-nitrotoluene, there has been only a small 'demand so that itpresented adisagreeable waste-product in the chemical industry.Therefore, the discovery of a roup of dye stufis, having such excellentastness properties and at the same time providing a use tfor thisproduct, is-cf very great imporance.

Ewamples.

1. The material is padded with a solution of 20 g. 2.3-hydroxynaphthoicllCld-O-tOllllg. water, 550 g. tragacanth (60:1000) and to this areadded before using: 20 g. sodium acetate; total, 1 kg.

The dyestufi has formula:

the following fiructural 0H off-1a 2. The material is padded with asolution of: 20 g. 2.3-hydroxynaphthoic acid-o-toluidid, 60 g. causticsoda solution of 22 Be, 20 g. para soap PN, made up to'l liter.

Then it is dried and printed with the following colour: 12.7 g.p-chlor-anilin, 200 g.

water, 24 cc. hydrochloric acid of 22 Be, mix well to a aste, cool With150 g. ice, then add 8 g. sodium nitrite dissolved in 50 g. water,- 550tragacanth (60:1000) and to this are added before using: 20 g. sodiumacetate; total, 1 kg.

The dyestufi' has the following structural formula:

on on:

3. The material is padded with a solution of: 20 g. 2.3-hydroxyna8hthoicacid-4- chlor-o-toluidid (CI-I NH: 1:1 :2 4c) 65 g. caustic sodasolution of 22 B., 20 g. s-

dium ricinolate, made up to 1 liter.

Then it is dried and printed with the following colour-t- 16.8 g. 4nitro-o-anisidin are dissolyed wiliffiO cc. hydrochloric acid of 22 B.and 200 cc. boiling water, well cooled and then added 150 g. ice. Tothis is added while stirring 7 .2 g. sodium nitrite dissolved in cc.water. The solution is made up with water to 500 g.

This diazo-solution is mixed with 480 g. tragacanth (:1000) and to thisare added before using: 20 g. sodium acetate crystallined; total, 1 kg.

, Thus is obtained a very bright-red I n the fibre of'very good fastnessproperties The dyestufi has the following structural formula:

OCH:

-N ll N a 4. The material is padded with a solution of: 27 g.2.3-hydroxynaphthoic acid-4- brom-o-toluidid, 60 g. caust c sodasolution of 22 B., 20 g. parasoap PN, made up to 1 liter.

Then .it is dried and printed with the following colour: 15.7 g.p-chloranisidin, 20G Water, 24 cc. hydrochloric of 22 13 mix well to apaste, cool with 150 ice, then add 8 g. sodium nitrite dissolv in 50 g.water, 550 tragacanth (60:1000) and'to this are added before iisingi 20g. sodium acetate; total, 1 kg.

The dyestufi formula 5. Padding liquor: 23 g. 2.3-hydro'xynaphthoicacid-5-chlor-o-to luidid, 60 g. caustic soda solution 22 B.,-boilingwater, 20 g. para soap PN, to l liter.

Printing aste: 17.5 g. 4;chlor-3-toluidine hydrochlori e, 200 g. water,16g. hydrochloric acid of 22? B., dissolve, cool with 150 cc. ice, thenadd 7 g.,sodium nitrite dissolved in 50 g.. water,540 g. tragacanth (60:1000) and before use add 20 g. sodium acetate; total, 1kg.

has that allowing structural eeaeeo The dyestuii has the followingstructural formula:

- chlor o -toluidine 'h drochloride are dissolved with 16 cc. hyochloric acid 22 Be. and 200 cc. boiling water, then cooled while adding150 g. ice. To this is added a solution of 7.2 g. nitrite in 50 cc.water while stirring. The solution is made up to 4 liter and to thisadded 20 g. acetate before use.

After (1 eing it is well wrung, rinsed and soaped. his is obtained averybright red of excellent fastness r0 rties.

, The dyestufi has t e ollowing structural formula 1.

7. The diazo-coln und obtained ir'd m 141.1 g. chlor-o-tolui e in theusual manner, is ured in an aqueous suspension oi 29 g..3-hydroxynaphthoic acid-o-toluidid prepared by dissolving it in causticsoda sc= lution and again precipitating it with thluted acetic acid. Thedyestu separates in blulsh-red flakes; then is filtered, washed Thedyestufi has the following structural and dried.

' formula Having now described my invention what mil) 1. As new produotethe am dyestuffs of 2.15 the m a mn the general formula: V i

the 2.8-h ydroxynaphthoio 'ncid and which "Fun-cam I 9 f.

nd hydrochloric acid to an aromatic-amine any diazo compounds derivedfrom mononu-.

which'can be obtained by the combination of clear nromatio amines .witho-tolnidides of 15 I by reduction-with stannoua ehloridl wherein R inaybe any niononiiclear aromatio imd town toluidideof the1-amino-2-hydtoxy-- residue, X ma be hydrogen, halogen or any3-,naphth0ic acid;- 7. substituent, is a met yl position to thenitrogen.

HERMANN WAGNER.

group in ortho Q; Inte'stimony whereof,I am: my signature.

